Cocatalyst compositions



United States Patent p 3,392,160 COCATALYST COMPOSITIONS AdamOrzechowski, Waltham, Mass., assignor to Cabot Corporation, Boston,Mass., a corporation of Delaware No Drawing. Continuation-impart ofapplication Ser. No. 305,515, Aug. 29, 1963. This application Feb. 7,1964, Ser. No. 343,204 The portion of the term of the patent subsequentto Jan. 18, 1982, has been disclaimed 19 Claims. (Cl. 260-94.3)

ABSTRACT OF THE DISCLOSURE The present invention provides novelcatalysts for the polymerization and copolymerization of olefinicmonomers. The catalyst is generally characterized as comprising theproduct of reaction between (1) the product of reaction between a GroupIVa, Va or VIa transition metal amine, and a finely-divided particulatesolid bearing hydroxyl groups on the surface thereof, and (2) variousorganometallic activators. The olefin monomer is polymerized bycontacting thereof with said catalyst under various conditions.

Accordingly, it is a principal object of the present invention toprovide new and useful catalyst components.

It is another object of the present invention to provide a novelpolymerization process.

It is still another object of the present invention to provide novelpolymerization catalysts.

Other objects of the present invention will in part be obvious and willin part appear hereinafter.

This application is a continuation in part of copending U.S.application, Ser. No. 305,515, filed Aug. 29, 1963, now abandoned, andUS. application Ser. No. 86,868, filed Feb. 3, 1961, now US. 3,166,542.

In accordance with the present invention, monoand di-olefins arepolymerized or copolymerized by a catalyst comprising (a) the product ofthe reaction carried out under certain conditions between certain aminecompounds of Groups IVa, Va and VIa metals and hydroxyl groups on thesurface of a finely-divided particulate solid and (b) an organometalliccompound. The polymerization or copolymerization reaction can beefiected at suitable temperatures within the range of from about -25 C.to about 250 C., and pressures from below atmospheric upwardly to anydesired maximum pressure, for example, 30,000 p.s.i.g. or even higherpressures.

Solids suitable for the purposes of the present invention generallyinclude any compound which is available in finely-divided particulateform with hydroxyl groups on the surface thereof. For example, oxidessuch as silica, alumina, zirconia, thoria and magnesia, silicates suchas chrysotile, actinolite and crocidolite, aluminates such as corundumand bauxite and carbon black such as channel black are all generallysuitable for purposes of the present invention. It should be noted thatthe ultimate efliciency of the catalyst components produced inaccordance with the present invention is generally highly dependent uponthe number of surface 'hydroxyl groups present per gram offinely-divided solid. Accordingly, in preparing the transitionmetallated finely-divided solids of the present invention, it should bekept in mind that the smaller the average particle size of the solid andthe larger the quantity of hydroxyl groups on the surface thereof, thegreater will be the potential activity and efficiency of the catalystcomponent producible therefrom. Therefore, it is important to use as thestarting material particulate, finely-divided solids having an averageparticle diameter of less than about 1 micron, and preferably less thanabout 0.1 micron, and a surface hydroxyl group concentration of at least3,392,160 Patented July 9, 1968 "ice about l 1O and preferably of atleast about 5 X 10- equivalents per gram.

Amine compounds of Groups IVa, Va and VIa metals, hereinafter referredto as transition metal compounds, suitable for the purposes of thepresent invention are those compounds conforming to the empiricalformula X T (NR wherein each X is any halogen; a is a number from 0 to3; T is a metal of Group IVa, Va and VIa (Mendeleev Periodic System);each N is nitrogen; each R is hydrogen or any hydrocarbon radical offrom about 1 to '8 carbon atoms in length; q is a number from 1 to 6'.

Specific examples of R groups for substitution in the above formulainclude methyl, ethyl, propyl, isobutyl, 2-ethylcyclohexyl,l-methylpentyl; 2,3-dimethylbutyl; methylethyl; octyl; 2-methyl-2-butyland l methylheptyl.

Specific examples of compounds conforming to the formula which aresuitable for the purposes of the present invention aretetrakisdiethylaminotitanium-Ti[N(C H 1 tetrakisdipentylaminotitaniumTi['N(C H tetrakisdimethylaminozirconium Zr[N(CH trisdiethylamino (mono)dimethylaminotitaniumte trakismethylpropylaminozirconiuma) 3 014trisdipentylamino (monomethylethylaminovanadiumpentakisdibutylaminoniobium-Nb [N(C Hdichlorodibutylaminotitanium- (C H N] TiCIbromotrisdipentylaminozirconium- (C H N] ZrBr;tetrakisdiethylaminochromium-Cr[N(C H and the like.

The conditions under which reaction between the transition metalcompound and the finely-divided solid can be accomplished are subject toconsiderable variation. However, in order to obtain a catalyst componentwith exceptionally high activity and reproducible character andperformance it has been found to be all important that thefinely-divided solid be essentially dry and anhydrous (i.e. free ofmolecular water in any form) at the time it is brought into contact withthe transition metal compound. In addition, it is recommended thatreaction of the solid and the transition metal compound be accomplishedso as to allow by-products of the reaction to be eliminated from thereaction zone in order to thereby insure that said reaction goes tocompletion. Generally, the said reaction can be carried out bycontacting said solid with said transition metal compound, preferably ina solution thereof in an inert hydrocarbon medium, and maintaining thetwo reactants in intimate contact for a period of time sufficient toelfect the desired chemical reaction resulting in the chemical bondingof the transition metal to an oxygen atom(s) in the surface of thesolid.

Elimination of the by-products of the reaction from the reaction zone,i.e. from the reaction medium, can be accomplished in any convenientmanner such as, by sweeping the reaction vessel with an inert gas, bycarrying out the reaction at sufiiciently elevated temperatures whilestirring to drive off by-products, and by complexing or reacting saidby-products with suitable substances.

Generally speaking, almost any temperature between about 0 C. and about300 C. and even higher temperatures can be used satisfactorily,providing that the decomposition temperatures of the compounds utilizedis not exceeded, but 25 C. to about C. is generally preferred. Assumingprovision is made for intimate contact of the dry solid and thetransition metal compound,

the minimum time required to accomplish the chemical reaction will varyfrom periods of the order of about 10 hours at C. to periods of theorder of about 30 minutes at temperatures of 100 C. or over.Temperatures substantially higher than about 300 C., are generallycompletely needless and therefore of little or no interest.

Of course, the reaction can also be carried out by other means, such asby exposing the solid to the vapors of the transition metal compound,provided, of course, that said solid is exposed to sufficient quantitiesof the vapors of said compound under conditions of time and temperaturethat will foster reaction. Said vapors can be supplied under their ownvapor pressures using partial vacuum if necessary, or with the aid of adry, inert carrier gas such as nitrogen. This vapor phase treatment canbe accomplished in any suitable manner such as by circulating the vaporsthrough the particulate solid in a fixed or moving bed reactor.

It is believed, though there is no intention to be bound by thisexplanation, that the type of reaction that occurs is correctlyillustrated by the following illustrative equations, wherein silicarepresents the finely-divided solids and tetrakisdimethylaminotitaniumrepresents the transition metal compounds:

-siioH S[i-O organometallic compounds suitable for the purposes of thepresent invention are the compounds chosen from the group consisting of(a) compounds conforming to the empirical formula wherein M is a metalchosen from Groups I, II and HI of the periodic table; M is a metal ofGroup I of the periodic table; v is a number from 0 to 1; each X is anyhalogen; n is a number from 0 to 3; each R is any monovalent hydrocarbonradical or hydrogen; y is a number from 1 to 4; and wherein yn equals atleast one; and

(b) compounds conforming to the empirical formula wherein each R" ischosen from the group consisting of monovalent hydrocarbon radicals,monovalent alkoxy radicals, monovalent aryloxy radicals, and thehalogens; p is a number from 0 to 3; each H is a hydride radical; m is anumber from 1 to 4; S is chosen from the group consisting ofquadrivalent silicon, germanium, tin and lead; and O is oxygen.

Specific examples of R" groups for substitution in the above formulainclude methyl; 2-methyl-2-butenyl; ndodecyl; 4 cyclohexylethyl;methylnaphthylethyl; 2,2,1- bicycloheptyl; tolyl; xylyl; xenyl; methoxy;isobutoxy; noctyloxy; phenoxy and l,2-naphthoxy.

Specific examples of compounds conforming to the formula aresilane-SiH,,; ethylsilane-H SiC H diethylmonochloro- 4 silane-HSiCl(C Hdichlorosilane H SiC1 methyldiethylsilane-HSi C H CHtrimethoxysilane-HSi (OCH 3 tribenzylsilane-HSi CH C Hdicyclohexylphenylsilane- 5(C5H11) 2; tIiPherl0XySi1aIle-HSi(OC H5) 3;triphenylgermane- (C H GeH;

tricyclohexylgermane-(C H hGeH tribenzylgermane (C H CH 3GCH;ethylisoamylgermane- (C2H5) (i-C5H11) GeHg dibutylstannane- (C H SnHdi-isopropylstannane (iC I-l' SnH tripentylstannane- (C H SnH;n-butylgermane n-C H GeH triphenylplumbane-(C H PbH; triethoxystannane-(C H O SnH;

1,2-dihydrotetramethylstannoxane- (CH HSn0SnH(CH cyclic alkyl hydrogensilicones such as (CH HSIO) and linear alkyl hydrogen silicones such as(CH HSiOSiH (CH 2 Organometallic compounds which conform to the formulaMM' X -R' and which are suitable for the practice of the inventioninclude compounds conforming to the subgeneric formula wherein M is aGroup I, II or III metal, such as sodium, beryllium, boron, aluminum andgallium; wherein k is a number from 1 to 3 depending upon the valency ofM; and wherein each R is hydrogen or any monovalent hydrocarbon radical.Examples of suitable hydrocarbon radicals include aryl or alkarylradicals, aliphatic hydrocarbon radicals, or derivatives, such as alkyl,cycloalkenylalkyl, arylalkyl, alkylcycloalkyl and cycloalkylalkenyl.

Specific examples of R of groups for substitution in the above formulainclude methyl, isobutyl, hexyl, ndodecyl, 2-methyl-2-butenyl,4-bicycloheptyl, dimethylcyclohexyl, S-cyclopentadienyl,phenylcyclohexyl, tolyl, xylyl, xenyl, and dimethylnaphthyl.

Specific compounds conforming to the empirical formula and which aretherefore suitable for the purposes of the present invention are organocompounds such as butyllithium, di-p-tolylmercury, tri-n-amylboron,triisobutylaluminum, diisobutylaluminum bromide, phenylmercuric iodide,hexylcupric chloride, octylmagnesium hydride, triethyllithium aluminumbromide and sodiumdiphenyllithium. Definitely preferred, however, arethe aluminum alkyls such as aluminum triisobutyl.

Further specific examples of suitable organometallic compoundsconforming to the formula can be found in copending U.S. application,Ser. No. 278,414 filed May 6, 1963, by Orzechowski and Mac- Kenzie.

It is pointed out that catalysts formed with the organometalliccompounds of the present invention conforming to the formula such as thesilanes, for example, often require activation by heating, in the caseof the silanes to temperatures above about C. and preferably above aboutC. for at least about 1 hour. At higher temperatures, shorter periods oftime are required. At substantially lower temperatures, the catalyst iseither not formed at all or is of inferior quality. The temperaturesthat need be utilized in activating the catalyst with any particularcombination of components can be readily determined bearing in mind thattemperatures (or pressures) that cause substantial decomposition ofeither of the components of the catalyst should be avoided.

Although it is appreciated that when R or R" in the above empiricalformulae do not comprise at least one hydrocarbon radical, the resultingcompounds cannot normally be termed organometallic compounds, compoundslacking at least one hydrocarbon radical comprise such a relativelysmall number of compounds included by said general formulae that for thepurposes of the present invention, it is intended that these compoundsbe included within the generic term, organometallic compound.Accordingly, in the present specification and claims, it is intended,and therefore, it should be understood, that the term, organometalliccompound, refers to all the compounds included Within the scope of theabove defined general formulae. In addition, it is pointed out thatwhile, strictly speaking, silicon and germanium are not metals, it isintended, and therefore it should be understood, that for the purposesof the present specification and claims, silicon and germanium aremetals and the term organometallic includes within its scope, siliconand germanium compounds within the scope of the above formula,

Using the catalysts of this invention, polymerization andcopolymerization of olefinic monomers can often be accomplished in theabsence of liquids other than the monomers themselves, solvents ordiluents, for example, in the gas phase, but it is usually moreconvenient to effect polymerization in the presence of a substantiallyinert liquid reaction medium. Accordingly, an inert liquid reactionmedium is preferably supplied to the reaction zone.

Several classes of hydrocarbons or their mixtures which are liquid andsubstantially inert under the polymerization conditions of the presentprocess constitute suitable liquid reaction media. Thus, various classesof saturated hydrocarbons such as pure alkanes or cycloalkanes orcommercially available mixtures, freed of harmful impurities, aresuitable for the purposes of the present invention. For example,straight run naphthas or kerosenses containing alkanes and cycloalkanesand liquid or liquefied alkanes such as n-hexane, 2,3-dimethylbutane,n-dodecane, dirnethylcyclopentane, methyldecalins, and the like aresuitable. Also, members of the aromatic hydrocarbon series, such asisopropyl benzene, ethyltoluene, hemimellitene, pseudocumene, isodurene,isoarnylbenzene, and particularly the mono-nuclear aromatic hydrocarbonssuch as xylenes, mesitylene and xylene-p-cymene mixtures, and the likeare completely suitable.

The proportion of transition metallated finely-divided solid toorganometallic compound utilized in preparing the finished catalyst isnot usually a critical feature of the process. -Moreover, if thisproportion is expressed as a simple molar or weight ratio, it may not beparticularly meaningful because as indicated above, the efiiciency ofsaid surface reacted solids (on a weight or molar bases) is highlydependent upon the proportion of transition metal having amine radicalsattached thereto which is chemically attached to the surface of thesolids. Accordingly, in order to be most meaningful, the relationshipbetween amounts of the two components of the finished catalyst should beexpressed as some function of the amount of transition metal, which ischemically attached to the surface of the finely-divided solid. We havefound from experience that an atomic ratio of from 0.1 to and preferably0.3 to 5 of the organometallic compound to transition metal chemicallyattached to the surface of the finely-divided solid is desirable.

The quantity of catalyst, i.e., comprising both the surface reactedfinely-divided solid and the organometallic compound to be utilized inthe polymerization reaction may vary, the precise quantity selected foruse being dependent upon the desired rate of polymerization, thegeometry of the reaction zone, the composition of the particularolefinic charging stock, temperature and other reaction variables. Itshould be pointed out that in general the efiiciency of the catalysts ofthe present invention is of a high order and accordingly, the totalquantity of catalyst that need be employed based on the Weight of thecharging stock is small particularly when a very fine particle sizemetal or metalloid oxide (preferably pyrogenic) has been utilized as thefinely-divided solid.

Harmful impurities in the liquid hydrocarbon reaction medium can beeffectively neutralized prior to the formation therein, or additionthereto, of the catalyst or catalyst components of this invention bytreating the liquid medium with a metal alkyl or a transition metalcompound. The olefinic charging stocks can also be purified by any knownmeans such as bubbling said stocks through a solution of a metal alkylin a hydrocarbon solvent prior to their introduction into thepolymerization reactor.

Temperature control during the course of the polymerization process canbe readily accomplished when a liquid hydrocarbon diluent is utilizedbecause of the presence in the reaction zone of a large liquid masshaving relatively high heat capacity. The liquid hydrocarbon reactionmedium can, in turn, be cooled by indirect heat exchange with a suitablecoolant inside or outside the reaction zone.

The contact time or space velocity employed in the polymerizationprocess will be selected with reference to the other process variablessuch as the particular catalysts utilized, the specific type of productdesired, and the extent of monomer conversion desired in any given runor pass over the catalyst. In general, this variable is readilyadjustable to obtain the desired results.

There follow a number of illustrative non-limiting examples:

Example 1 To a 2000 milliliter, glass, three neck reaction flaskequipped with a stirrer and condenser there is charged 20 grams ofCab-O-Sil, a pyrogenic silica produced by Cabot Corporation, and whichhas an average particle diameter of about 10 millimicrons and a hydroxylgroup content on the surface thereof about 1.5 milliequivalents pergram. Next, there is added to said vessel 1650 milliliters ofethylbenzene and the resulting slurry is dried by being heated to, andmaintained at, the boiling point of ethylbenzene, i.e. about 137 C., forabout 24 hours while a water/ethylbenzene azeotrope is removed from thereaction vessel by periodic distillation until 450 milliliters ofdistillate has been removed. The vessel is then cooled and charged with20 millimoles of tetrakisdi-n-propylaminotitanium; Ti[N(nC H Theresulting slurry is then heated to, and maintained at, refluxingtemperature for about 16- hours with continuous stirring while beingswept by a stream of dry nitrogen. Subsequently, the extent of thereaction between the tetrakisdi-n-propylaminotitanium and hydroxylgroups on the surface of the silica is determined by measuring thequantity of di-n-propylamine that was produced and by testing the liquidcontent of the vessel for the absence therein oftetrakisdi-n-propylaminotita nium, and the said silica is found to have20 milliatoms of titanium bound to the surface thereof. 180 millilitersof this slurry containing about 3 millimoles of titanium chemicallybound to the surface of about 3 grams of silica, is then transferredfrom this reaction vessel to a 500 cc. stainless steel bomb which hasbeen previously flushed with dry nitrogen. Next, said bomb is chargedwith 9 millimoles of triisobutylaluminnm followed by pressurization to2.00 p.s.i. with ethylene. The bomb is then heated to and maintained at,about C. for 6 hours with continuous agitation, while a pressure ofabout 200 p.s.i. is maintained therein by the periodic addition ofethylene. Subsequently, the solid reaction products are analyzed and itis found that solid polyethylene has been produced.

7 Example 2 To a 2000 milliliter, three neck, glass reaction vesselthere is added 20 grams of Alon, a pyrogenic alumina produced byDeutsche Goldund Silber-Scheideanstalt vormals Roessler, and which hasan average particle diameter of about -40 millimicrons and a hydroxylgroup content on the surface thereof of about 0.7 milliequivalents pergram. Next, there is added to said vessel 1500 milliliters of n-hexaneand the resulting slurry is dried azeotropically for 20 hours untilabout 500 milliliters of a water/n-hexane azeotrope have been removed.The vessel is then cooled to ambient temperature and charged with 9millimoles of tetrakisdimethylaminozirconiumZr [N (CH3 2] 4 Theresulting slurry is then refluxed at about 80 C for about 46 hours 'withcontinuous stirring while being swept by a stream of dry nitrogen.Subsequently, the extent of reaction between thetetrakisdimethylarninozirconium and the hydroxyl grousp on the surfaceof the alumina is determined by measuring the quantity of dimethylaminethat 'was produced and by testing the liquid con-tents of the vessel forthe absence therein of tetrakisdimethylaminozirconium, and the saidalumina is found to have 9 milliatoms of zirconium chemically bound tothe surface there of. A 333 milliliter portion of this slurry containingabout 3 milliatoms of zirconium bound to the surface of about 6.7 gramsof alumina is then transferred, without exposure to the atmosphere, to a1000 milliliter stainless steel, reaction bomb. There is then charged tosaid bomb 2S millimoles of triethylsilane previously dissolved in 100milliliters of anhydrous benzene. The bomb is then sealed, heated to andmaintained at about 155 C. and continuously agitated for about 8 hours.Next, there is charged to said bomb 400 millimoles of isoprene monomer.Said bomb is then continuously stirred at a temperature of about 80 C.for 4 hours. The reaction products are analyzed and it is found thatsolid polyisoprene has been formed.

Example 3 To a 2000 milliliter, three neck, glass reaction vessel thereis added 20 grams of Supercarbovar, a channel carbon black produced byCabot Corporation, which has an average particle diameter of 14millimicrons and a by droxyl group content on the surface thereof ofabout 1.6 milliequivalents per gram. To said reaction vessel there isadded 1700 milliliters of benzene, and the resulting slurry is dried bybeing heated to, and maintained at, the refluxing point of benzene, i.e.about 80 C., for about 20 hours, while a water/ benzene azeotrope isremoved from the reaction vessel by periodic distillation until about450 milliliters of distillate has been removed. The vessel is thencooled and charged with 20 millimoles oftetrakisdiethylaminozirconium-Zr[N(C H 1 The resulting slurry is thenrefluxed for about 6 hours with continuous stirring while being swept bya stream of dry nitrogen. Subsequently, the extent of the reactionbetween the tetrakisdiethylaminozirconium and the hydroxyl groups on thesurface of the carbon black is determined by measuring the quantity ofdiethylamine that is produced and by testing the liquid contents of thevessel for the absence therein of tet-rakisdiethylarninozirconium, andsaid slurry is found to contain 20 milliatoms of zirconium chemicallybound to the surface of said barbon black.

125 milliliters of this slurry containing about 2 milliatoms ofzirconium bound to the surface of about 2 grams of carbon black is thencharged to a 500 milliliter stainless steel reaction bomb. Next, thereis charged to said bomb about 4 millimoles of triethylstannane and thebomb is then sealed and agitated at a temperature of about 80 C. forabout two hours. Thereafter, after cooling to about 0 C., there isintroduced into the bomb 50 millimoles of 1,3-butadiene and 50millimoles of ethylene. The bomb is then heated to, and maintained at,about C. with continuous agitation for about 8 hours. Subsequentanalysis of the solid product reveals that an ethylenebutadienecopolymer has been produced.

It is also found that other carbon blacks having a similar hydroxylgroup concentration on the surface thereof yield similar results.

The polymers produced by the catalysts of the present invention can besubjected to such aftertrea-tment as may be desired to fit them forparticular uses or to impart desired properties. Thus, the polymers canbe extruded, mechanically milled, filmed or cast, or converted tosponges or latices. Also, antioxidants, stabilizers, fillers such ascarbon black, silicas, extenders, plasticizers, pigments, insecticides,fungicides, etc., can be incorporated into the polymers.

Obviously, many changes can be made in the above described examples andprocedures without departing from the scope of the invention. Forexample, although only titanium and zirconium compounds are utilized inthe above examples, other compounds such as vanadium compounds are alsosuitable for the purposes of the present invention. For example,

pentakisdi-i-propylaminonio'biumNb [N(i-C H 5 andtetrakisdiethylaminochromium-Cr[N(C H are entirely suitable.

Also, pyrogenically coforme-d, or coprecipitated metal oxides, or metaloxides coformed with, or mixed with, other compounds are suitable forthe purposes of the present invention when the particle size and surfacehydroxyl group concentration thereof is within the limits set forthhereinbefore.

Accordingly, it is intended that the above disclosure be regarded asillustrative and as in no way limiting the scope of the invention.

What I claim is:

1. A catalyst component comprising a finely-divided solid carrying inchemical combination surface structures conforming to the formulawherein each X is any halogen; a is a number from 0 to 3; T is a metalchosen from the group consisting of Groups IVa, Va and VIa; each N isnitrogen; each R is hydrogen or a hydrocarbon radical of from 1 to 8carbon atoms in length; and q is a number from 1 to 5; and wherein saidstructures are chemically linked directly from T to at least one oxygenatom in the surface of said solid.

2. The catalyst component of claim 1 wherein T is a metal of Group Na.

3. The catalyst component of claim 1 wherein T is titanium.

4. The catalyst component of claim 1 wherein T is zirconium.

5. The catalyst component of claim 1 wherein T is a metal of Group Va.

6. The catalyst component of claim 1 wherein T is vanadium.

7. The catalyst component of claim 1 wherein T is a metal of Group VIa.

8. The catalyst component of claim 1 wherein T is chromium.

9. The catalyst component of claim 1 wherein in said formula, (1 is 0.

10. The catalyst component of claim 1 wherein said solid is a metaloxide having an average particle diameter of less than about 0.1 micronand a concentration of said structures on the surface thereof of atleast about 1 x10" equivalents per gram.

11. The catalyst component of claim 10 wherein said solid is chosen fromthe group consisting of silica and alumina.

12. A catalyst which comprises the product of reaction between (1) afinely-divided solid carrying in chemical combination surface structuresconforming to the formula:

wherein each X is any halogen; a is a number from O to 3; T is a metalchosen from the group consisting of Groups IVa, Va and VIa; each N isnitrogen; each R is hydrogen or a hydrocarbon radical of from 1 to 8carbon atoms in length; and q is a number from 1 to 5, and where saidstructures are chemically linked directly from T to at least one oxygenatom on the surface of said solid, and

(2) an organometallie compound chosen from the group consisting ofcompounds conforming to the general formulae:

where M is a metal chosen from Groups i, II and 111 of the periodictable; M is a metal of Group I of the periodic table; v is a number from0 to 1; each X is any halogen; n is a number from 0 to 3; each R ischosen from the group consisting of any monovalent hydrocarbon radicaland hydr gen; y is a number from 1 to 4; and wherein y-n equals at leastone; and compounds conforming to the formula:

wherein each R" is chosen from the group consisting of any monovalenthydrocarbon radical, monovalent alkoxy radical, monovalent aryloxyradical, and the halogens; p is a number from 0 to 3; each H ishydrogen; m is number from 1 to 4; S is chosen from the group consistingof a quadrivalent metal of lVb; and O is oxygen.

13. The catalyst of claim 12 wherein said organometallic compoundconforms to the formula I R i fll 14. The catalyst of claim 12 whereinin the formula II R 1Hmso S is silicon.

15. The catalyst of claim 12 wherein said organometallic compoundconforms to the formula 16. The catalyst of claim 12 wherein saidorganometallic compound is an aluminum alkyl.

17. A process for polymerizing a substance chosen from the groupconsisting of a mono-olefin, mixtures of mono-olefins, a di-olefin,mixtures of di-olefins and mixtures thereof which comprises contactingsaid substance at temperatures between about -25 C. and 250 C., with acatalyst comprising (a) a finely-divided solid carrying in chemicalcombination surface structures conforming to the formula:

X T(NR wherein each X is any halogen; a is a number from O to 3; T is ametal chosen from the group consisting of Groups IVa, Va and VIa; each Nis nitrogen; each R is hydrogen or a hydrocarbon radical of from 1 to 8carbon atoms in length; and q is a number from 1 to 5, and wherein saidstructures are chemically linked directly from T to at least one ox genatom in the surface of said solid, and

(b) an organometallic compound chosen from the group of compoundsconforming to the general formulae:

wherein M is chosen from the group consisting of the metals of Groups I,II and III; M is a metal of Group I; v is a number from 0 to 1; each Xis any halogen; n is a number from 0 to 3; each R is chosen from thegroup consisting of any monovalent hydrocarbon radical and hydrogen; yis a number from 1 to 4; and wherein y-n is at least one, and

wherein each R" is chosen from the group consisting of any monovalenthydrocarbon radical, monovnlent, alkoxy radical, monovalent aryloxyradical and the hologens; p is a number from 0 to 3; each H is hydrogen;m is a number from 1 to 4; S is chosen from the group consisting ofquadrivalent metals of Group Nb; and O is oxygen. 18. The process ofclaim 16 wherein the substance to be polymerized is analpha-mono-olefin.

19. The process of claim 1.6 wherein the substance to be polymerized isa di-olefin which has a double bond in the alpha position.

References Cited UNITED STATES PATENTS 3,166,542 1/1965 Orzechowski etal. 26094.9

3,166,543 1/1965 Orzechowski et al. 26094.9

3,196,137 7/1965 Cain 260-949 OTHER REFERENCES Perry: DieMakromolekulare Chemie, 65, 145-456 (19-63).

JOSEl H L. SCHOFER, Primary Examiner.

W. HOOVER, R. A. GAITHER, Assistant Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,392,160 July 9, 1968 Adam Orzechowski et a1.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below:

In the heading to the printed specification, line 3, "Adam Orzechowski,Waltham, Mass., assignor to" should read Adam Orzechowski, Waltham,Mass., and James C. MacKenzie, Rochester,

N. Y. assignors to Signed and sealed this 2nd day of December 1969.

(SEAL) Attest:

Edward M. Fletcher, Jr. WILLIAM E. SCHUYLER,

Attesting Officer Commissioner of Patents

